CN105579407A - Glass plate and chemically strengthened glass plate - Google Patents

Glass plate and chemically strengthened glass plate Download PDF

Info

Publication number
CN105579407A
CN105579407A CN201480053107.0A CN201480053107A CN105579407A CN 105579407 A CN105579407 A CN 105579407A CN 201480053107 A CN201480053107 A CN 201480053107A CN 105579407 A CN105579407 A CN 105579407A
Authority
CN
China
Prior art keywords
glass
fluorine
sheet glass
mole
warpage
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201480053107.0A
Other languages
Chinese (zh)
Inventor
井川信彰
宫坂聪史
白井正信
三浦丈宜
加藤亮祐
山中一彦
林泰夫
谷井史朗
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of CN105579407A publication Critical patent/CN105579407A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/007—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in gaseous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B18/00—Shaping glass in contact with the surface of a liquid
    • C03B18/02—Forming sheets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
  • Glass Compositions (AREA)

Abstract

The present invention relates to a glass plate in which the fluorine content within the glass is greater than 0.23 mol%/[mu]m and equal to or less than 21 mol%/[mu]m in a depth-direction profile which is obtained by secondary ion mass spectroscopy (SIMS) and exhibits a horizontal axis expressing depth and a vertical axis expressing fluorine concentration (mol%). The glass plate according to the present invention enables warpage subsequent to chemical strengthening to be effectively suppressed and abrasion processing, etc., prior to chemical strengthening to be omitted or simplified.

Description

Sheet glass and chemically reinforced glass plate
Technical field
The present invention relates to sheet glass and chemical enhanced chemically reinforced glass plate has been carried out to described sheet glass.
Background technology
In recent years; in the panel display apparatus such as mobile phone or portable information terminal (PDA), Personal Computer, televisor, vehicle mounted guidance display unit; in order to protect indicating meter and improve attractive in appearance, the front of having carried out thin tabular protective glass to be configured in indicating meter is to reach the region wider than image displaying part.
Owing to requiring light weight and slimming for such panel display apparatus, therefore also require the thinning protective glass for indicating meter protection.
But during the thickness of thinning protective glass, intensity reduces, sometimes cause protective glass self to break because of dropping in using or in carrying etc., thus there is the problem of the original effect that cannot play protection display unit.
Therefore, existing protective glass forms compressive stress layer on surface by carrying out chemical enhanced to the glass utilizing float glass process to manufacture (following, to be sometimes referred to as float glass), improves the traumatic resistance of protective glass thus.
Report the situation (patent documentation 1 ~ 3) that float glass causes flatness impaired in chemical enhanced rear generation warpage.Think that this warpage is produced by following reason: the glass surface (hereinafter also referred to end face) do not contacted with the molten metal such as molten tin when float forming and the different in kind of glass surface (hereinafter also referred to bottom surface) contacted with molten metal, cause the chemical enhanced degree (entering リ side) of carrying out on two sides different.
Chemical enhanced degree of carrying out is stronger, and the warpage of described float glass is larger.Therefore, in the requirement in order to meet for high damnification resistant, bearing stress is adjusted to more than degree up to now, especially more than 600MPa, the problem of warpage becomes more obvious.
Patent Document 1 discloses by forming SiO at glass surface 2enhancement method that is chemical enhanced, that regulate the glass of the amount of the ion entering glass when chemical enhanced is thus carried out after film.In addition, disclose in patent documentation 2 and 3 by the bearing stress of top surface side is set in specified range reduce chemical enhanced after the method for warpage.
In addition, in the past, in order to reduce the problem of described warpage, carry out following countermeasure: reduce by the enhancement stress of chemical enhanced generation, or carry out chemical enhanced after removing surface heterogeneous medium layer by carrying out ground or milled processed etc. at least one face of glass.
Prior art document
Patent documentation
Patent documentation 1: U.S. Patent Application Publication No. 2011/0293928 specification sheets
Patent documentation 2: No. 2007/004634th, International Publication
Patent documentation 3: Japanese Laid-Open Patent Publication 62-191449 publication
Summary of the invention
Invent problem to be solved
But, describedly in patent documentation 1 form SiO at glass surface 2carry out after film in chemical enhanced method, preheating condition time chemical enhanced is restricted, and likely causes SiO in addition according to condition 2the film quality of film changes and has an impact to warpage.In addition, as described in patent documentation 2 and 3, the bearing stress of top surface side being set in the method in specified range, have problems from the viewpoint of the intensity of glass.
In addition, carry out in the method for ground or milled processed etc. at least one face of glass before chemical enhanced, from the viewpoint of the existing problems that boost productivity, preferably omit these ground or milled processed etc.
In addition, when warpage more than chemical enhanced rear generation to a certain degree, when printing the black surround of protective glass, the gap sometimes between glass and worktable becomes excessive and makes glass not be adsorbed in worktable.In addition, when protective glass one-piece type for contact panel, in subsequent handling, carry out the film forming such as ITO (IndiumTinOxide, indium tin oxide) with the state of large template sometimes.Now, the air knife producing glass and medical liquor treating trough or rinse bath sometimes to contact etc. and transports exception or warpage increases in ITO film forming, causes the film-forming state of the ITO in substrate periphery portion improper, thus the unfavorable condition such as to be peeling.In addition; at LCD (LiquidCrystalDisplay; liquid-crystal display) and the protective glass being pasted with contact panel between the type of Existential Space when, when protective glass exists the warpage to a certain degree, produce brightness disproportionation, Newton's rings sometimes.
Therefore, the object of the present invention is to provide a kind of can effectively suppress chemical enhanced after warpage, simultaneously can omit or simplify chemical enhanced before the sheet glass of milled processed etc.
For the means of dealing with problems
The present inventor finds: by being conceived to carry out fluorine amount (total importing fluorine amount) contained in the glass after fluoridation to glass surface, and fluorine amount contained in described glass is set in certain scope, can reduce thus chemical enhanced after warpage.The present invention is completed based on this discovery.
That is, the present invention is as follows.
1. a sheet glass, wherein, transverse axis is being set to the degree of depth and is being set to by the longitudinal axis on the depth direction distribution curve obtained by SIMS analysis (SIMS) of Funing tablet (% by mole), fluorine amount contained in glass is greater than 0.23 % by mole μm and is less than or equal to 21 % by mole μm.
2. the sheet glass as described in preceding paragraph 1, wherein, fluorine amount contained in described glass is more than 0.7 % by mole μm and less than 9 % by mole μm.
3. the sheet glass as described in preceding paragraph 1, wherein, described glass is soda lime glass, and fluorine amount contained in described glass is more than 0.7 % by mole μm.
4. the sheet glass as described in preceding paragraph 3, wherein, fluorine amount contained in described glass is less than 17 % by mole μm.
5. the sheet glass as described in preceding paragraph 1, wherein, described glass is alumina silicate glass, and fluorine amount contained in described glass is for being greater than 0.23 % by mole μm and being less than or equal to 7 % by mole μm.
6. the sheet glass as described in preceding paragraph 5, wherein, fluorine amount contained in described glass is less than 6 % by mole μm.
7. the sheet glass according to any one of preceding paragraph 1 ~ 6, its sheet glass for being manufactured by float glass process.
8. the sheet glass according to any one of preceding paragraph 1 ~ 7, its thickness is below 1.5mm.
9. the sheet glass according to any one of preceding paragraph 1 ~ 8, its thickness is below 0.8mm.
10. the sheet glass according to any one of preceding paragraph 1 ~ 9, its surface roughness Ra is below 2.5nm.
11. 1 kinds of chemically reinforced glass plates, it obtains by carrying out chemical enhanced to the sheet glass according to any one of preceding paragraph 1 ~ 10.
12. 1 kinds of panel display apparatus, it is the panel display apparatus possessing protective glass, and wherein, described protective glass is the chemically reinforced glass plate described in preceding paragraph 11.
Invention effect
For sheet glass of the present invention, glass, in certain scope, can be adjusted to desired value by the chemical enhanced stress value obtained by fluorine amount thus contained in the glass in the distribution of depth direction that it is obtained by SIMS.In addition, though simplify or omit chemical enhanced before milled processed etc., also can reduce chemical enhanced after the warpage of glass, thus obtain excellent planeness.
Accompanying drawing explanation
The typical Funing tablet distribution curve obtained by SIMS of the alumina silicate glass after Fig. 1 (a) ~ (c) represents fluoridation.
Fig. 2 (a) represents in the manufacture of sheet glass utilizing float glass process, utilizes crossbeam supply containing the gas that there is the molecule of fluorine atom in its structure and outline figure to the method that the surface of glass ribbon processes.The A-A sectional view that Fig. 2 (b) is Fig. 2 (a).
Fig. 3 (a) ~ (d) represents and the amount of gas can be divided into 3 parts on the width of glass ribbon and carry out the sectional view of the crossbeam regulated.
Fig. 4 is the figure schematically showing the double-current method injector that can use in the present invention.
Fig. 5 is the figure schematically showing the single current injector that can use in the present invention.
Fig. 6 for chemical enhanced float glass of the present invention carry out chemical enhanced after, as the sectional view of the flat-panel monitor of cover glass for flat panel displays.
Fig. 7 is the figure representing the method calculating fluorine amount contained glass from SIMS distribution curve.
Fig. 8 is the figure of fluorine amount contained in the glass of the sheet glass of the present invention (alumina silicate glass) that expression is obtained by SIMS and the relation of this glass being carried out to the warp displacement amount after chemical intensification treatment (anti-リ addendum modification).
Fig. 9 is the figure of fluorine amount contained in the glass of the sheet glass of the present invention (soda lime glass) that expression is obtained by SIMS and the relation of this glass being carried out to the warp displacement amount after chemical intensification treatment.
Figure 10 (a) represents the typical Funing tablet distribution curve obtained by SIMS of alumina silicate glass.Figure 10 (b) represent with the degree of depth for transverse axis, with the arbitrfary point x shown in formula (a) ithe slope at place is that the longitudinal axis carries out the figure obtained that maps.The figure that Figure 10 (c) expression dotted portion amplified in Figure 10 (b) amplifies and obtains.
Embodiment
1. sheet glass
The present invention relates to a kind of sheet glass, wherein, transverse axis is being set to the degree of depth and is being set to by the longitudinal axis on the depth direction distribution curve obtained by SIMS analysis (SIMS) of Funing tablet (% by mole), fluorine amount contained in glass is greater than 0.23 % by mole μm and is less than or equal to 21 % by mole μm.
In the present invention, so-called " sheet glass ", also comprises and makes melten glass be configured as tabular and the sheet glass that obtains.Sheet glass chemical enhanced after warpage be because of a face of sheet glass and chemical enhanced in another face to carry out degree different and produce.Specifically, such as, in the case of float glass, chemical enhanced in the glass surface (end face) do not contacted with molten metal (being generally tin) when float forming and the glass surface (bottom surface) contacted with molten metal carries out degree difference, produce thus chemical enhanced after warpage.
According to the present invention, by fluorine amount (total importing fluorine amount) contained in glass being set in certain scope to sheet glass carrying out fluoridation, the velocity of diffusion of the ion in a face of sheet glass and another face can be regulated thus, and make the chemical enhanced degree of carrying out in a face and another face become balanced.Therefore, sheet glass of the present invention without the need to regulating enhancement stress or carry out the process such as grinding and grinding before chemical intensification treatment, namely can reduce chemical enhanced after the warpage of sheet glass.
As can be able to reduce by carrying out fluoridation to the surface of sheet glass chemical enhanced after the mechanism of warpage, think that generation has following phenomenon.
(1) promote to relax by being directed into the fluorine on the surface of glass, the CS (compressivestress, bearing stress) in the face after fluoridation is reduced.
(2) suppress ion-exchange by being directed into the fluorine on the surface of glass, the DOL (depthoflayer, the stress degree of depth) in the face after fluoridation is reduced.
(3) dealkalize of glass is produced by fluoridation.
(4) made by fluoridation the main component of glass surface change, make Si in glass with SiF 4or H 2siF 6form reduce from glass surface, therefore the generation degree (entering リ side) of stress changes.
(5) suppressed by fluoridation from the dehydration of glass surface or water is immersed, reducing warpage thus.
Sheet glass of the present invention is the degree of depth when to be set to glass surface by transverse axis be zero and is set to by the longitudinal axis on the depth direction distribution curve obtained by SIMS analysis (SIMS) of Funing tablet (% by mole), and fluorine amount contained in glass is greater than 0.23 % by mole μm and is less than or equal to the sheet glass of 21 % by mole μm.
Fluorine amount contained in so-called glass, as shown in Figure 7, can by the degree of depth (μm) when transverse axis is set to glass surface by the depth direction distribution curve in SIMS is zero, the longitudinal axis is set to Funing tablet (% by mole) time integration (% by mole μm) obtain.About the method for calculation of the Funing tablet in SIMS, will carry out later describing.
Fluorine amount contained in so-called glass, although be accurately the amount of fluorine atom contained in sheet glass entirety, but owing to thinking that the fluorine caused by fluoridation can be invaded and there is the limit to the degree of depth in glass, therefore in fact can be considered as and be the value that integrated value that the depth direction till 0 ~ 30 μm distributes when measuring is identical to starting at the degree of depth from glass surface.
Think fluorine amount contained in glass (% by mole μm) with the warp displacement amount (μm) after chemical intensification treatment carried out to this glass there is a proportionlity (Fig. 8 and Fig. 9).At this, so-called warp displacement amount, can be obtained by formula shown below.
Warp displacement amount=Δ X-Δ Y
Δ X: the chemical enhanced caused warpage variable quantity of undressed sheet glass
Δ Y: the chemical enhanced caused warpage variable quantity of treated sheet glass
Herein, warpage variable quantity be the amount of warpage of sheet glass after chemical enhanced deduct chemical enhanced before the value that obtains of the amount of warpage of sheet glass.For warpage variable quantity, be set to Δ X > 0.For Δ Y, when along the direction warpage identical with Δ X, be set to Δ Y > 0, when along the direction warpage contrary with Δ X, be set to Δ Y < 0.
If fluorine amount contained in glass is in above-mentioned scope, then regardless of the kind of this glass, all can improve chemical enhanced after warpage.Wherein, the glass manufactured by float glass process improves effect due to visible more warpages, therefore preferably.
Sheet glass of the present invention is when for sheet glass after chemical enhanced, transverse axis is being set to the degree of depth (μm) and is being set to by the longitudinal axis on the depth direction distribution curve obtained by SIMS analysis (SIMS) of Funing tablet (% by mole), fluorine amount contained in glass is also greater than 0.23 % by mole μm and is less than or equal to 21 % by mole μm.
Sheet glass of the present invention can contain fluorine on two sides, also only can contain fluorine in a face.Wherein, from the viewpoint of improving warpage, be preferably the latter.
It should be noted that, in this manual, a face of so-called sheet glass and another face, refer to a face relative on thickness of slab direction and another face.In addition, the two sides of so-called sheet glass, refers to two sides relative on thickness of slab direction.
Next, the method obtaining Funing tablet (% by mole) in SIMS analysis (SIMS) is described.
The isotropic substance M of the element M in SIMS analysis 1secondary ions intensity I m1with primary ions intensity I p, the sputtering raste Y of matrix, the concentration C of element M m(ratio relative to total concn), isotropic substance M 1there is probability α 1, element M secondary ions rate β mand it is mass spectrometric proportional through efficiency eta (comprising the detection efficiency of detector).
I m1=AI pyC mα 1β mη (formula 1)
Herein, A is the ratio of area of detection relative to the sweep limit of primary ions bundle of secondary ions.Typically, owing to being difficult to the η obtaining device, therefore β cannot be obtained mabsolute value.Therefore, by the main component element in same sample etc. being used as with reference to element and obtaining the ratio with (formula 1), and cancellation η.
At this, when being set as R with reference to element, its isotropic substance being set as Rj, can obtain (formula 2).
I m1/ I rj=(C mα 1β m)/(C rα jβ r)=C m/ K (formula 2)
Herein, K is the relative sensitivity factor of element M relative to element R.
K=(C rα jβ r)/(α 1β m) (formula 3)
In this case, the concentration of element M is obtained by (formula 4).
C m=KI m1/ I rj(formula 4)
In the present invention, F corresponds to M 1, Si corresponds to R j.Therefore, according to (formula 2), both strength ratio (F/Si) and Funing tablet C mthe value obtained divided by K is equal.
The result of the Funing tablet measure of spread from the glass utilizing above-mentioned SIMS device, and calculate average concentration of fluorine by following steps (a1) ~ (a3).Fig. 1 (a) ~ (c) represents the typical Funing tablet distribution curve obtained by SIMS of the alumina silicate glass after fluoridation.
(a1) Funing tablet obtained by the SIMS distribution of the known standard test specimen of concentration and determination object sample is measured [Fig. 1 (a)].
(a2) by the measurement result production standard curve of standard test specimen, and calculate in order to incite somebody to action 19f/ 30si is converted to the coefficient [Fig. 1 (b)] of Funing tablet (% by mole).
(a3) Funing tablet (% by mole) of determination object sample is obtained by the coefficient calculated in operation (a2).The value [Fig. 1 (c)] that such as, average concentration of fluorine (% by mole) within the scope of the degree of depth obtained by SIMS 0 ~ 3 μm obtains for the Funing tablet within the scope of the accumulation degree of depth 0 ~ 3 μm and divided by the degree of depth 3 μm.
Also the average concentration of fluorine (% by mole) of the degree of depth 0 ~ 30 μm obtained by SIMS can similarly be obtained.
Integrated value this Funing tablet (% by mole) being set to the longitudinal axis, when the degree of depth (μm) being set to transverse axis is defined as fluorine amount contained in glass (% by mole μm).
As the analysis condition of SIMS, such as, can enumerate following condition.It should be noted that, analysis condition shown below is example, suitably should change according to determinator, sample etc.In addition, the degree of depth of the transverse axis of the depth direction distribution curve obtained by sims analysis can be obtained by utilizing the degree of depth of contact pin type film thickness gauge (such as Wei Yike Inc. Dektak150) determination and analysis pit.
(analysis condition)
Primary ions kind: Cs +
Primary ions input angle: 60 °
Acceleration voltage a: 5kV
As analysis condition more specifically, such as, can enumerate following condition.
(analysis condition)
Determinator: the SIMS analysis device with quadrupole mass spectrometer
Primary ions kind: Cs +
Acceleration voltage a: 5.0kV
Primary ions electric current: 1 μ A
Primary ions input angle (angle apart from sample face vertical direction): 60 °
Raster size: 200 × 200 μm 2
Surveyed area: 40 × 40 μm 2
Secondary ions polarity: negative
The electron beam gun of neutralization uses: have
As the SIMS analysis device with quadrupole mass spectrometer, such as, can enumerate the ADEPT1010 of ULVAC-PHI Inc..
Fluorine amount contained in the glass of sheet glass of the present invention is generally and is greater than 0.23 % by mole μm and is less than or equal to 21 % by mole μm, from the viewpoint of improving warpage, is more preferably more than 0.7 % by mole μm and less than 9 % by mole μm.
But the preferable range of fluorine amount is different according to the composition of glass, when soda lime glass, is more preferably more than 0.7 % by mole μm and less than 21 % by mole μm, more preferably more than 0.7 % by mole μm and less than 17 % by mole μm.
In addition, when glass is alumina silicate glass, is more preferably and is greater than 0.23 % by mole μm and is less than or equal to 7 % by mole μm, be more preferably greater than 0.23 % by mole μm and be less than or equal to 6 % by mole μm.
Herein, about the details of the composition of glass, will carry out later describing.
The thickness of sheet glass is not particularly limited, and can enumerate such as: 2mm, 0.8mm, 0.73mm, 0.7mm, 0.56mm, 0.4mm; In order to effectively carry out chemical intensification treatment described later, being usually preferably below 5mm, being more preferably below 3mm, more preferably below 1.5mm, being particularly preferably below 0.8mm.
The sheet glass of usual required thickness 0.7mm chemical enhanced after amount of warpage be less than 40 μm.In the sheet glass that 90mm is square, CS is 750MPa, DOL when being 40 μm, and the amount of warpage after chemical enhanced is about 130 μm.On the other hand, square there is inverse proportional relation due to the amount of warpage of the sheet glass after chemical enhanced and thickness of slab, therefore the amount of warpage when thickness of sheet glass is 2.0mm is about 16 μm, warpage does not become problem in fact.Therefore, be less than 2mm at the thickness of sheet glass, when typically being below 1.5mm, likely produce chemical enhanced after the problem of warpage.
Sheet glass of the present invention is the sheet glass that the Funing tablet in a relative in a thickness direction face is greater than the Funing tablet in another face, and preferably meets following formula (1).
1≤x…(1)
(in formula (1), x is in the Funing tablet distribution curve obtained by SIMS, any degree of depth x ithe slope at (μm) place meets the full depth (μm) of following formula (2))
[F(x i+0.1)-F(x i)]/0.1＝-0.015…(2)
(in formula (2), F (x i) represent degree of depth x ithe Funing tablet (% by mole) obtained by SIMS at (μm) place)
Figure 10 (a) represents the typical Funing tablet distribution curve obtained by SIMS of alumina silicate glass.Figure 10 (b) for the degree of depth for transverse axis, with the arbitrfary point x shown in following formula (a) ithe slope at place is that the longitudinal axis carries out the figure obtained that maps.In following formula (a), F (x) represents the Funing tablet (% by mole) at some x place.
[F(x i+Δx)-F(x i)]/Δx…(a)
When Δ x is set to 0.1, the slope shown in formula (a) be-0.015 full depth x (μm) be preferably more than 1, be more preferably more than 2, more preferably more than 2.8, be particularly preferably more than 3.When x is less than 1, the displacement of warpage does not observe significant difference.
Figure 10 (c) is for amplifying the dotted portion of the figure of Figure 10 (b) and the figure that obtains.Such as, in Figure 10 (c), when Δ x is set to 0.1, the full depth x (μm) when the slope shown in formula (a) is-0.015 is 6.5.
2. the manufacture method of sheet glass
In the present invention, the method making melten glass be configured as the sheet glass of tabular is not particularly limited, and in addition, as long as this glass is have the glass that can be carried out the composition strengthened by chemical intensification treatment, then can use various composition.Such as, can manufacture in the following way: prepare various raw material in right amount and heating and melting, then homogenized by deaeration or stirring etc., and be configured as tabular by known float glass process, glass tube down-drawing (such as scorification etc.) or pressing etc., be cut into desired size after slow cooling, and implement attrition process.In these manufacture method, the glass manufactured by float glass process due to be easy to especially play as effect of the present invention chemical enhanced after warpage improve, therefore preferably.
As the sheet glass used in the present invention, specifically, the sheet glass such as typically comprising soda lime glass, alumina silicate glass, borate glass, lithium alumina silicate glass, borosilicate glass can be enumerated.
Among those, the glass of the composition containing Al is preferably.When Al and alkali coexist, form 4 coordinations and participate in the cancellated formation of the skeleton becoming glass in the same manner as Si.When the Al of 4 coordinations increases, the movement of basic ion becomes easy, thus ion-exchange is easy to carry out when chemical intensification treatment.
As the composition of sheet glass of the present invention, can be set forth in by % by mole represent form in containing 50 ~ 80% SiO 2, 0.1 ~ 25% Al 2o 3, 3 ~ 30% Li 2o+Na 2o+K 2the ZrO of O, the MgO of 0 ~ 25%, the CaO of 0 ~ 25% and 0 ~ 5% 2glass, be not particularly limited.More specifically, the composition of following glass can be enumerated.It should be noted that, such as, so-called " MgO containing 0 ~ 25% " though refer to that MgO is nonessential and contain, can at most containing 25% implication.It should be noted that, in the present invention, the glass of following (i) belongs to soda lime glass, and the glass of following (ii) and (iii) belongs to alumina silicate glass.
(i) by % by mole represent form in containing 63 ~ 73% SiO 2, 0.1 ~ 5.2% Al 2o 3, 10 ~ 16% Na 2o, 0 ~ 1.5% K 2the glass of O, the MgO of 5 ~ 13% and the CaO of 4 ~ 10%
(ii) by % by mole represent form the SiO containing 50 ~ 74% 2, 1 ~ 10% Al 2o 3, 6 ~ 14% Na 2o, 3 ~ 11% K 2the ZrO of O, the MgO of 2 ~ 15%, the CaO of 0 ~ 6% and 0 ~ 5% 2, and SiO 2and Al 2o 3content add up to less than 75%, Na 2o and K 2the content of O add up to the content of 12 ~ 25%, MgO and CaO add up to 7 ~ 15% glass
(iii) by % by mole represent form the SiO containing 68 ~ 80% 2, 4 ~ 10% Al 2o 3, 5 ~ 15% Na 2o, 0 ~ 1% K 2o, the MgO of 4 ~ 15% and the ZrO of 0 ~ 1% 2glass
(iv) by % by mole represent form the SiO containing 67 ~ 75% 2, 0 ~ 4% Al 2o 3, 7 ~ 15% Na 2o, 1 ~ 9% K 2o, the MgO of 6 ~ 14% and the ZrO of 0 ~ 1.5% 2, and SiO 2and Al 2o 3content add up to 71 ~ 75%, Na 2o and K 2the content of O add up to 12 ~ 20%, be less than the glass of 1% containing its content during CaO
In the manufacture method of sheet glass of the present invention, make containing at least one face that there is the gas of the molecule of fluorine atom or liquid (hereinafter referred to as fluorine-containing fluid) and sheet glass or glass ribbon in its structure contacts and carry out surface treatment.
Under carrying out surface-treated situation making fluorine-containing fluid contact with at least one face of glass ribbon, the surface temperature of glass ribbon is preferably more than 600 DEG C, is more preferably and is greater than 650 DEG C.By being set greater than 650 DEG C, and be easy to enough to reduce chemical enhanced after the total Exposure of fluorine of amount of warpage of glass obtained glass is implemented to the winding-up process of fluorine-containing fluid.It should be noted that, below, sometimes this term of sheet glass is brought use as general designation sheet glass and glass.
As fluorine-containing fluid, can enumerate such as: hydrogen fluoride (HF), freonll-11 (such as fluorochlorohydrocarbon, fluorocarbon, Hydrochlorofluorocarbons, hydrogen fluorohydrocarbon, Kazakhstan dragon (halon)), hydrofluoric acid, fluorine simple substance, trifluoroacetic acid, tetrafluoro-methane, silicon tetrafluoride, phosphorus pentafluoride, phosphorus trifluoride, boron trifluoride, nitrogen trifluoride, chlorine trifluoride etc.; But be not limited to these gases or liquid.
Among those, from the viewpoint of high with the reactivity of glass pane surface, be preferably hydrogen fluoride, freonll-11 or hydrofluoric acid.In addition, also can two or more in these gases used in combination.In addition, when glass is manufactured with a float process, when jetting fluorine-containing fluid to glass ribbon, because float tank internal oxidition power is excessively strong, therefore preferably fluorine simple substance is not used.
In addition, when using liquid, such as can be supplied to glass pane surface by spraying with liquid former state state, also can be supplied to glass pane surface by after vaporizing liquid.In addition, other liquid or gas also can be utilized as required to dilute.
As fluorine-containing fluid, also can containing fluid except these fluids except, preferably at normal temperatures not with the fluid of molecular reaction that there is fluorine atom.
As above-mentioned fluid, can enumerate such as: N 2, air, H 2, O 2, Ne, Xe, CO 2, Ar, He and Kr etc., but be not limited to these.In addition, also can two or more in these gases used in combination.
As the carrier gas of fluorine-containing fluid, preferably use N 2, the rare gas element such as argon gas.In addition, SO can also be contained in fluorine-containing fluid 2.SO 2use when producing sheet glass continuously by float glass process etc., have prevent transport roller in slow cooling region with contact glass sheet and make glass produce the effect damaged.In addition, also can containing the gas at high temperature decomposed.
In addition, also water vapor or water can be comprised in fluorine-containing fluid.Water vapor can obtain at rare gas elementes such as bubbling nitrogen, helium, argon gas, carbonic acid gas in warmed-up water.When needing a large amount of water vapors, also method water being fed through vaporizer and direct boiling can be adopted.
By fluorine-containing fluid is jetted to glass or glass ribbon, fluorine can be made to invade from glass surface, thus obtain fluorine-containing glass.
Need to regulate fluorine contained in the glass making to obtain to the condition of the fluorine-containing fluid of winding-up be greater than .23 % by mole μm and be less than or equal to 21 % by mole μm.
Such as, in float glass process to glass ribbon jet fluorine-containing fluid and fluorine is invaded, from the viewpoint of reducing for the load of equipment, the fluorine atom concentration in fluorine-containing fluid is preferably 0.1 volume % ~ 15 volume %, is more preferably 0.1 volume % ~ 10 volume %.
For the surface temperature of glass ribbon, when the second-order transition temperature of this sheet glass is set to Tg, be preferably (Tg+50) DEG C ~ (Tg+460) DEG C, be more preferably (Tg+150) DEG C ~ (Tg+460) DEG C, more preferably (Tg+230) DEG C ~ (Tg+460) DEG C.
When jetting fluorine-containing fluid to glass ribbon, although by winding-up fluorine-containing fluid and make fluorine invade in glass, to making glass ribbon slow cooling manufacturing float glass plate during in, a part for the fluorine sometimes invaded is escaped in glass.
But in purport of the present invention, the fluorine amount due to this escape is trace, so there is no the technical necessity distinguished with the fluorine atom concentration in the float glass after forming process the fluorine atom concentration in glass ribbon.
In the present invention, as the concrete example making melten glass be configured as the method for the sheet glass of tabular, float glass process is described in detail.In float glass process, use have to frit carry out melting melting furnace, make melten glass float over molten metal (tin etc.) upper and formed glass ribbon float tank and this glass ribbon is carried out slow cooling leer glass manufacturing apparatus and manufacture sheet glass.
When molten metal (tin) bath makes forming of glass, also can supply fluorine-containing fluid from the side (end face) in non-contacting metal face to the sheet glass transported on bath of molten metal and this glass pane surface be processed.In slow cooling region after the bath of immediately molten metal (tin), sheet glass is transported by roller.
At this, so-called slow cooling region, not only refers in leer, also comprises the part from transporting in above-mentioned molten metal (tin) bath to being transported in leer in comfortable float tank.In slow cooling region, also can supply this gas from the side of non-contacting molten metal (tin).
Fig. 2 (a) represents in the manufacture of sheet glass utilizing float glass process, supplies fluorine-containing fluid and outlines figure to the method that glass surface processes.
Floating over molten metal (tin etc.) making melten glass is above formed in the float tank of glass ribbon 101, is jetted fluorine-containing fluid to this glass ribbon 101 by the crossbeam 102 be inserted in float tank.As shown in Fig. 2 (a), the side-jetting of fluorine-containing fluid preferably from the non-contacting molten metal face of glass ribbon 101 is to glass ribbon 101.Arrow Ya represents the direction that glass ribbon 101 flows in float tank.
For the position of fluorine-containing fluid of jetting for glass ribbon 101 by crossbeam 102, when second-order transition temperature is more than 550 DEG C, the temperature of glass ribbon 101 is preferably (Tg+50) DEG C ~ (Tg+460) DEG C, be more preferably (Tg+150) DEG C ~ (Tg+460) DEG C, more preferably (Tg+230) DEG C ~ (Tg+460) DEG C.The temperature of preferred glass ribbon is different according to the kind of the fluid of winding-up, the fluorine amount that can be increased in obtained glass by winding-up greater concn at a higher temperature and/or more substantial fluid in principle.
In addition, the position of crossbeam 102 can be the upstream of radiation weir plate (ラ ジ エ mono-シ ヨ Application ゲ mono-ト) 103, also can in its downstream.When HF, the amount of jetting to the fluorine-containing fluid of glass ribbon 101 is preferably 1 × 10 -6~ 5 × 10 -3mole/glass ribbon 1cm 2.
Fig. 2 (b) represents the A-A sectional view of Fig. 2 (a).By crossbeam 102 from the direction winding-up of Y1 to " entering " inflow certainly of the fluorine-containing fluid of glass ribbon 101, and flow out from the direction of " going out ".That is, the direction along arrow Y4 and Y5 is moved and is exposed to glass ribbon 101.In addition, the fluorine-containing fluid along the direction movement of arrow Y4 flows out from the direction of arrow Y2, and the fluorine-containing fluid along the direction movement of arrow Y5 flows out from the direction of arrow Y3.
Also exist chemical enhanced after the situation that changes according to the position of the width of glass ribbon 101 of the amount of warpage of sheet glass, in such cases, preferably regulate the amount of fluorine-containing fluid.That is, preferably increase the amount of fluorine-containing fluid of jetting in the position that amount of warpage is large, and reduce the amount of the fluorine-containing fluid of winding-up in the position that amount of warpage is few.
The amount of warpage of the sheet glass after chemical enhanced changes according to the position of glass ribbon 101, can by being can in the structure of the fluorine-containing Fluid Volume of the adjusted width-wise of glass ribbon 101 by the configuration settings of crossbeam 102, thus in the adjusted width-wise amount of warpage of glass ribbon 101.
As concrete example, the amount of fluorine-containing fluid will be divided into 3 parts of I ~ III on the width 110 of glass ribbon 101 and the sectional view carrying out the crossbeam 102 regulated is shown in Fig. 3 (a).Gas system 111 ~ 113 is split by dividing plate 114,115, and flows out fluorine-containing fluid from gas hole 116 respectively and jet to glass.
Arrow in Fig. 3 (a) represents the flowing of fluorine-containing fluid.Arrow in Fig. 3 (b) represents the flowing of the fluorine-containing fluid in gas system 111.Arrow in Fig. 3 (c) represents the flowing of the fluorine-containing fluid in gas system 112.Arrow in Fig. 3 (d) represents the flowing of the fluorine-containing fluid in gas system 113.
As the method fluorine-containing fluid being supplied to by sheet glass to glass surface, the method such as using injector and the method etc. using ingress pipe can be enumerated.
The schematic diagram being used for the surface-treated injector of sheet glass that can use in the present invention is marked in Fig. 4 and Fig. 5.Fig. 4 is the figure schematically showing the double-current method injector that can use in the present invention.Fig. 5 is the figure schematically showing the single current injector that can use in the present invention.
Fluorine-containing fluid sprays towards sheet glass 20 from central slit 1 and outer slit 2, and is flowed through on sheet glass 20 by stream 4, and is exhausted from exhaust slot 5.It should be noted that, the symbol 21 in Fig. 4 and Fig. 5 is the direction that sheet glass 20 flows, parallel with stream 4.
When the fluorine-containing fluid supplied by injector is gas, the gas vent of injector and the distance of sheet glass are preferably below 50mm.
By above-mentioned distance is set as below 50mm, gas can be suppressed to diffuse in air, and for desired gas volume, the gas of substantial amount can be made to arrive sheet glass.On the contrary, time too short with the distance of sheet glass, such as, when carrying out online treatment to the sheet glass by float process, sheet glass is likely caused to contact with injector because of the variation of glass ribbon.
In addition, when the fluorine-containing fluid supplied by injector is liquid, the liquid spraying outlet of injector and the distance of sheet glass are not particularly limited, as long as the configuration for processing sheet glass equably.
Injector can use any one mode such as double fluid or single current, also can in series arrange more than 2 along the flow direction of sheet glass and process glass pane surface.So-called double-flow injection device, as shown in Figure 4, refers to and is equally divided into forward and reverse injector to the moving phase of the gas of exhaust for the travel direction of sheet glass from ejection.
This double-flow injection device is common double-flow injection device, also known as the double-flow injection device used for the manufacture of low-reflection glass.Such as, sometimes use as follows: to the soda lime glass (second-order transition temperature 560 DEG C) of the Asahi Glass reheated to the thickness 1.8mm of 600 DEG C, from central slit 1 with flow velocity 64cm/ to jet second be heated to 150 DEG C by HF gas 1.12SLM (with the aerometer per minute under standard state rise number) and nitrogen (N 2) gas that mixes of 9SLM, and to jet N from outer slit 2 2gas 45.5SLM.Surfaceness (arithmetic average roughness) Ra of glass surface of HF gas of jetting thus is 30.6nm, and the value of above-mentioned x is 2.5 μm.
So-called single current injector, as shown in Figure 5, for from ejection to the moving phase of the gas of exhaust forward is fixed on for the travel direction of sheet glass or reverse in the injector of either direction.When using single current injector, from the viewpoint of airflow stability, the flowing being preferably the gas on sheet glass is identical with the travel direction of sheet glass.
In addition, the two or more gas reaction in the supplying opening of fluorine-containing fluid, unreacted fluorine-containing fluid and the gas reacting with sheet glass and generate or fluorine-containing fluid and the venting port of the gas generated preferably are present on the face of the same side of sheet glass.
When carrying out surface treatment when supplying fluorine-containing fluid to glass pane surface in transit, such as, when sheet glass flows through on transfer roller, can supply from the side not contacting transfer roller.In addition, the Web materials that also can a part for the sheet glass such as guipure be used not to be capped by conveying belt, and the side certainly contacting transfer roller supplies.
In addition, also by the transfer roller in series arranging more than 2, and injector can be set between adjacent transfer roller, and supply this gas from the side of contact transfer roller and glass pane surface is processed.In addition, when sheet glass flows through on roller, can supply from the side of non-touch roll, also can supply between adjacent roller in the side of touch roll.
Identical or different gas can be supplied from the both sides of sheet glass.Such as, surface treatment can be carried out from this both sides supply gas of side of the side of non-touch roll and touch roll to sheet glass.Such as, in slow cooling region from the supply gas of both sides, injector can be configured to the glass transported continuously in the mode relative across sheet glass, and from the side of non-touch roll and this both sides supply gas of side of touch roll.
The injector being configured in the side of touch roll can be configured in different positions with the injector of the side being configured in non-touch roll on the flow direction of sheet glass.When being configured in different positions, relative to the flow direction of sheet glass, any one injector can be configured in upstream, also can be configured in downstream.
It is widely known that the sheet glass utilizing the glass manufacturing techniques of float glass process and CVD technology by combination and manufacture online with functional membrane.In this case known, nesa coating and basilar membrane thereof be all face supply gas from the face or non-touch roll that do not contact tin and film forming on a glass.
Such as, in the manufacture of the sheet glass with functional membrane of the online CVD of this utilization, at the face of touch roll configuration injector, and from this injector, fluorine-containing fluid can be supplied to sheet glass and glass pane surface is processed.
In addition, the pressure of glass pane surface when fluorine-containing fluid being supplied to glass pane surface is preferably from normal atmosphere-100Pa to the atmosphere of the pressure range of normal atmosphere+100Pa, is more preferably the atmosphere from normal atmosphere-50Pa to the pressure range of normal atmosphere+50Pa.
About gas flow, carry out describing typically to the situation using HF gas as fluorine-containing fluid.When utilizing HF gas processing sheet glass, HF gas flow is more, and it is larger that warpage during chemical intensification treatment improves effect, and therefore preferably, when total gas couette is identical, HF concentration is higher, and it is larger that warpage during chemical intensification treatment improves effect.
When total gas couette and HF gas flow are fixed, the time of process sheet glass is longer, and it is larger that warpage during chemical intensification treatment improves effect.Such as, when using HF gas to process glass pane surface after heating glass plate, the travelling speed of sheet glass is lower, and the warpage after chemical enhanced is more improved.Even if for the equipment of total gas couette, HF gas flow cannot be controlled well, also can by suitably control sheet glass travelling speed and improve chemical enhanced after warpage.
3. chemical enhanced
Chemical enhanced is at temperature below second-order transition temperature, by ion-exchange, alkalimetal ion (typically being Li ion or Na ion) little for the ionic radius of glass surface is exchanged for the large alkalimetal ion of ionic radius (typically being K ion), forms the process of compressive stress layer thus at glass surface.Chemical intensification treatment can be undertaken by existing known method.
In the present invention, by carrying out chemical enhanced to the sheet glass being imported with fluorine, can obtain chemical enhanced after the sheet glass that is improved of warpage.Sheet glass after chemical enhanced can utilize 3 d shape testing machine (such as Mitaka Kohki Co., Ltd.'s system) or surfaceness-outline shape measuring machine (such as Tokyo Seimitsu Co., Ltd's system) to measure relative to the variable quantity (warpage variable quantity) of the warpage of chemical enhanced front sheet glass.
In the present invention, the improvement of the warpage after chemical enhanced is except being undertaken in the experiment of other all identical conditions except surface treatment by fluorine-containing fluid, and the warp displacement amount obtained by utilizing formula shown below is evaluated.
Warp displacement amount (μm)=Δ X-Δ Y
Δ X: the chemical enhanced caused warpage variable quantity of undressed sheet glass
Δ Y: the chemical enhanced caused warpage variable quantity of treated sheet glass
Herein, the amount of warpage that warpage variable quantity is the sheet glass after chemical enhanced deduct chemical enhanced before the value that obtains of the amount of warpage of sheet glass.For warpage variable quantity, be set to Δ X > 0.For Δ Y, when along the direction warpage identical with Δ X, be set to Δ Y > 0, when along the direction warpage contrary with Δ X, be set to Δ Y < 0.
The chemical enhanced caused warpage variable quantity of undressed sheet glass depends on various condition, changes larger.Warp displacement amount is greater than prescribed value and means regardless of above-mentioned variation, all can control warpage.Therefore, warp displacement amount is prescribed value, is specifically that the sheet glass of more than 10 μm can reduce warpage issues.
The CS (bearing stress) of sheet glass and DOL (degree of depth of compressive stress layer) can utilize surface stress meter to measure.The bearing stress of chemically reinforced glass is preferably more than 600MPa, and the degree of depth of compressive stress layer is preferably more than 15 μm.By by the bearing stress of chemically reinforced glass and the depth-set of compressive stress layer within the scope of this, excellent intensity and traumatic resistance can be obtained.
4. panel display apparatus
Below, for sheet glass of the present invention is carried out chemical enhanced after, the example of protective glass that this chemically reinforced glass is used as panel display apparatus is described.Fig. 6 is the sectional view of the display unit being configured with protective glass.It should be noted that, in the following description, be oriented benchmark all around with the arrow in scheming.
As shown in Figure 6, display unit 40 possesses: be arranged on display panel 45 in housing 15 and with whole that covers display panel 45 and the protective glass 30 that arranges of the mode of surrounding the front of housing 15.
Protective glass 30 mainly improving the attractive in appearance of display unit 40 and intensity, prevent from impacting damaged etc. for the purpose of and arrange, the one piece of plate glass being general plane shape by global shape is formed.Protective glass 30 can be arranged in the mode (having the mode of gas cloud) be separated from the display side (front side) of display panel 45 as shown in Figure 6, also can be pasted on the display side of display panel 45 via the tacky film (not shown) with light transmission.
Emitting of protective glass 30, the front of the light of display panel 45 is provided with functional membrane 41, and at the back side of the light incidence from display panel 45, the position corresponding with display panel 45 is provided with functional membrane 42.It should be noted that, functional membrane 41,42 is arranged on two sides in figure 6, but is not limited to this, can be arranged on front or the back side, also can omit.
Functional membrane 41,42 has and such as prevents the reflection of surround lighting, prevents impacting breakage, shielding electromagnetic wave, shielding near infrared ray, revises tone and/or function such as raising traumatic resistance etc., and thickness and shape etc. are suitably selected according to purposes.Functional membrane 41,42 is such as formed by resin masking is pasted on protective glass 30.Or also can be formed by thin film forming method such as vapour deposition method, sputtering method or CVD.
Symbol 44 is black layer; such as by the Ink Application containing pigment particles is burnt till its irradiation ultraviolet radiation or heating in protective glass 30, then cools and the overlay film formed; make to observe display panel etc. from the outside of housing 15, thus improve the taste of outward appearance.
Thus, when the protective glass using sheet glass of the present invention as display unit, surfaceness (arithmetic average roughness) Ra is preferably below 2.5nm, more preferably below 1.5nm.Thus, the sharpness of the display image losing display unit because of protective glass can be prevented.The surface roughness Ra of sheet glass can measure as follows according to JISB0601 (calendar year 2001).Use the XE-HDM of AFM (AtomicForceMicroscope: atomic force microscope) such as ParkSystems company manufacture as determinator, measure 3 places, using the Ra value of the mean value at 3 places as sheet glass with scan size 1 μm × 1 μm.
Embodiment
Below, embodiments of the invention are specifically described, but the present invention is not limited to these embodiments.
(composition of sheet glass)
In the present embodiment, the sheet glass with the glass material A ~ D of following composition is used.
(glass material A) is % by mole to represent the SiO containing 72.0% 2, 1.1% Al 2o 3, 12.6% Na 2o, 0.2% K 2the glass (second-order transition temperature 566 DEG C) of O, the MgO of 5.5% and the CaO of 8.6%
(glass material B) is % by mole to represent the SiO containing 64.3% 2, 8.0% Al 2o 3, 12.5% Na 2o, 4.0% K 2o, 10.5% MgO, CaO, the SrO of 0.1% of 0.1%, the ZrO of the BaO of 0.1% and 0.5% 2glass (second-order transition temperature 604 DEG C)
(glass material C) is % by mole to represent the SiO containing 68.0% 2, 10.0% Al 2o 3, 14.0% Na 2the glass (second-order transition temperature 662 DEG C) of the MgO of O and 8.0%
(glass material D) is % by mole to represent the SiO containing 68.8% 2, 3.0% Al 2o 3, 14.2% Na 2the K of O, the CaO of 7.8%, the MgO of 6.2% and 0.2% 2the glass (second-order transition temperature 552 DEG C) of O
(mensuration of amount of warpage)
Before chemical enhanced, utilize SURFCOM surfaceness-outline shape measuring machine (Tokyo Seimitsu Co., Ltd's system) to measure amount of warpage, then carry out chemical enhanced to each glass, and similarly measure chemical enhanced after amount of warpage, and calculate the Δ amount of warpage (warpage variable quantity) shown in following formula.
Δ amount of warpage (warpage variable quantity)=chemical enhanced rear amount of warpage-chemical enhanced front amount of warpage
(warp displacement amount)
About the improvement of the warpage after chemical enhanced, be except utilizing fluorine-containing fluid to carry out in the experiment of other all identical conditions except surface treatment, the warpage variable quantity according to calculating above calculates warp displacement amount based on above-mentioned steps.
(SIMS analysis: SIMS)
The analysis condition of SIMS analysis is set as following.
Determinator: ULVAC-PHI Inc. ADEPT1010
Primary ions kind: Cs +
Acceleration voltage a: 5.0kV
Primary ions electric current: 1 μ A
Primary ions input angle (angle apart from sample face vertical direction): 60 °
Raster size: 200 × 200 μm 2
Surveyed area: 40 × 40 μm 2
Secondary ions polarity: negative
The electron beam gun of neutralization uses: have
Utilize above-mentioned formula 1 ~ formula 4 to obtain strength ratio (F/Si) according to obtained result, and then be converted to Funing tablet (% by mole).Make depth direction distribution curve transverse axis being set to the degree of depth, the longitudinal axis being set to Funing tablet (% by mole), and using contained in glass for its integrated value fluorine amount (% by mole μm).In addition, the invasion depth x of fluorine is obtained based on Funing tablet distribution curve.
In addition, the degree of depth of the transverse axis of the depth direction distribution curve obtained by sims analysis is obtained for utilizing the degree of depth of contact pin type film thickness gauge (Wei Yike Inc. Dektak150) determination and analysis pit.
(mensuration of bearing stress: CS and the stress degree of depth: DOL)
For obtained chemical enhanced after sheet glass in CS and DOL use the surface stress meter (FSM-6000LE) of Zhe Yuan manufacturing company to measure.
[embodiment 1-1 ~ 1-12 and comparative example 1]
(1) manufacture of float glass
Have in the float tank of glass material B in flowing, use HF gas to implement fluoridation (hereinafter referred to as HF process) as fluorine-containing fluid.By the HF concentration (volume %) of contacted gas and time (second) thereof and every 1cm of being calculated by these 2glass ribbon HF Exposure [the total Exposure of HF (mole/cm 2)] and the surface temperature (DEG C) of glass ribbon when the gas containing HF is contacted be shown in table 1.
In addition, making makes N 2float glass when gas replaces fluorine-containing fluid and contacts the surface of glass ribbon and respectively as with reference to (comparative example 1).
Utilize saltpetre melting salt, at 450 DEG C to the sheet glass after HF process and as with reference to and the sheet glass that do not import fluorine carries out 2 hours chemical intensification treatment, and measure warp displacement amount (μm) according to the Δ amount of warpage before and after chemical intensification treatment.Table 1 is shown in by about fluorine amount, the invasion depth x of fluorine and the evaluation result of warp displacement amount (μm) contained in glass.
Table 1
As shown in table 1, known: to carry out HF process by effects on surface and carry out after improving the Funing tablet in glass chemical enhanced, improve thus chemical enhanced after the warpage of sheet glass.In addition, according to the result of table 1, the relation of fluorine amount contained in glass and warp displacement amount is summarized in Fig. 8.There is a proportionlity in consequently contained in known glass fluorine amount and warp displacement amount.
In order to improve chemical enhanced after warpage, warp displacement amount is preferably more than 10 μm, known from the chart shown in Fig. 8: by fluorine amount contained glass is set greater than 0.23 % by mole μm, can effectively improve chemical enhanced after warpage.In addition, as shown in table 1, known: the invasion depth x (μm) of fluorine be the sheet glass of the embodiment 1-1 ~ 1-12 of more than 1 chemical enhanced after warpage be able to effective improvement.
[embodiment 2-1 ~ 2-6 and comparative example 2-1 ~ 2-2]
Glass material B is changed to glass material C, the time of chemical intensification treatment is set as 1.5 hours, in addition, carry out HF process, the chemical intensification treatment of glass ribbon in the mode identical with embodiment 1-1, and measure warp displacement amount (μm) according to the Δ amount of warpage before and after chemical intensification treatment.The invasion depth x of fluorine amount contained in the condition of HF process, glass, fluorine and warp displacement amount (μm) are shown in table 2.In addition, the time of chemical intensification treatment is set as 1.5 hours by comparative example 2-1 ~ 2-2, identical with comparative example 1 in addition, as reference.It should be noted that, in embodiment 2-1 ~ 2-6 and comparative example 2-1 ~ 2-2, compared with embodiment 1-1 ~ 1-12 and comparative example 1, the surface temperature (DEG C) of glass ribbon when setting makes the gas containing HF contact higher.
Table 2
As shown in table 2, known: to carry out HF process by effects on surface and carry out after improving the Funing tablet in glass chemical enhanced, improve thus chemical enhanced after the warpage of sheet glass.And known: by fluorine amount contained in glass is set greater than 0.23 % by mole μm, warp displacement quantitative change is more than 10 μm, can effectively improve thus chemical enhanced after warpage.In addition we know: the invasion depth x (μm) of fluorine be the sheet glass of the embodiment 2-1 ~ 2-6 of more than 1 chemical enhanced after warpage be able to effective improvement.
[embodiment 3-1 ~ 3-9 and comparative example 3]
Glass material B is changed to glass material A, the temperature of chemical intensification treatment is set as 420 DEG C, 2.5 hours will be set as the time, in addition, carry out HF process, the chemical intensification treatment of glass ribbon in the mode identical with embodiment 1-1, and measure warp displacement amount (μm) according to the Δ amount of warpage before and after chemical intensification treatment.The invasion depth x of fluorine amount contained in the condition of HF process, glass, fluorine and warp displacement amount are shown in table 2.In addition, comparative example 3 is that glass material B is changed to glass material A, and the temperature of chemical intensification treatment is set as 420 DEG C, will be set as 2.5 hours the time, identical with comparative example 1 in addition, as reference.
Table 3
As shown in Table 3; Carry out HF process by effects on surface and carry out after improving the Funing tablet in glass chemical enhanced, improve thus chemical enhanced after the warpage of sheet glass.In addition, according to the result of table 3, the relation of fluorine amount contained in glass and warp displacement amount is summarized in Fig. 9.There is a proportionlity in consequently contained in known glass fluorine amount and warp displacement amount.
In order to improve chemical enhanced after warpage, warp displacement amount is preferably more than 10 μm, the chart according to Fig. 9: by fluorine amount contained in glass is set as more than 0.7 % by mole μm, can effectively improve chemical enhanced after warpage.In addition, as shown in table 3, known: the invasion depth x (μm) of fluorine be the sheet glass of the embodiment 3-1 ~ 3-9 of more than 1 chemical enhanced after warpage be able to effective improvement.
[embodiment 4-1 ~ 4-4 and comparative example 4]
Glass material A is changed to glass material D, and carries out HF process, the chemical intensification treatment of glass ribbon in the mode identical with embodiment 3-1, and measure warp displacement amount (μm) according to the Δ amount of warpage before and after chemical intensification treatment.The invasion depth x of fluorine amount contained in the condition of HF process, glass, fluorine and warp displacement amount (μm) are shown in table 4.In addition, comparative example 4 is same with comparative example 3 is used as reference.It should be noted that, in embodiment 4-1 ~ 4-4 and comparative example 4, compared with embodiment 3-1 ~ 3-9 and comparative example 3, the surface temperature (DEG C) of glass ribbon when setting makes the gas containing HF contact higher.
Table 4
As shown in table 4, known: to carry out HF process by effects on surface and carry out after improving the Funing tablet in glass chemical enhanced, improve thus chemical enhanced after the warpage of sheet glass.In addition we know: by fluorine amount contained in glass is set as more than 0.7 % by mole μm, warp displacement quantitative change is more than 10 μm, can effectively improve thus chemical enhanced after warpage.In addition we know: the invasion depth x (μm) of fluorine be the sheet glass of the embodiment 4-1 ~ 4-4 of more than 1 chemical enhanced after warpage be able to effective improvement.
With reference to specific mode to invention has been detailed description, but to those skilled in the art it is clear that, can various change and correction be carried out when without departing from the spirit or scope of the invention.
It should be noted that, the Japanese patent application (Patent 2013-258466) that the Japanese patent application (Patent 2013-198474) that the application proposed based on September 25th, 2013, on December 13rd, 2013 propose and the Japanese patent application (Patent 2013-258467) that on December 13rd, 2013 proposes, and its entirety is quoted by way of reference to herein.
Reference numeral
1 central slit
2 outer slits
4 streams
5 exhaust slot
15 housings
20 sheet glass
30 protective glasses
40 display unit
41,42 functional membranes
45 display panels
101 glass ribbons
102 crossbeams
103 radiation weir plates
The width of 110 glass ribbons
111,112,113 gas systems
114,115 dividing plates
116 gas holes

Claims (12)

1. a sheet glass, wherein, transverse axis is being set to the degree of depth and is being set to by the longitudinal axis on the depth direction distribution curve obtained by SIMS analysis (SIMS) of Funing tablet (% by mole), fluorine amount contained in glass is greater than 0.23 % by mole μm and is less than or equal to 21 % by mole μm.
2. sheet glass as claimed in claim 1, wherein, fluorine amount contained in described glass is more than 0.7 % by mole μm and less than 9 % by mole μm.
3. sheet glass as claimed in claim 1, wherein, described glass is soda lime glass, and fluorine amount contained in described glass is more than 0.7 % by mole μm.
4. sheet glass as claimed in claim 3, wherein, fluorine amount contained in described glass is less than 17 % by mole μm.
5. sheet glass as claimed in claim 1, wherein, described glass is alumina silicate glass, and fluorine amount contained in described glass is greater than 0.23 % by mole μm and is less than or equal to 7 % by mole μm.
6. sheet glass as claimed in claim 5, wherein, fluorine amount contained in described glass is less than 6 % by mole μm.
7. the sheet glass according to any one of claim 1 ~ 6, its sheet glass for being manufactured by float glass process.
8. the sheet glass according to any one of claim 1 ~ 7, its thickness is below 1.5mm.
9. the sheet glass according to any one of claim 1 ~ 8, its thickness is below 0.8mm.
10. the sheet glass according to any one of claim 1 ~ 9, its surface roughness Ra is below 2.5nm.
11. 1 kinds of chemically reinforced glass plates, it is undertaken chemical enhanced by the sheet glass according to any one of claim 1 ~ 10 and obtains.
12. 1 kinds of panel display apparatus, it is the panel display apparatus possessing protective glass, and wherein, described protective glass is chemically reinforced glass plate according to claim 11.
CN201480053107.0A 2013-09-25 2014-09-22 Glass plate and chemically strengthened glass plate Pending CN105579407A (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP2013198474 2013-09-25
JP2013-198474 2013-09-25
JP2013258467 2013-12-13
JP2013-258466 2013-12-13
JP2013258466 2013-12-13
JP2013-258467 2013-12-13
PCT/JP2014/075013 WO2015046113A1 (en) 2013-09-25 2014-09-22 Glass plate and chemically strengthened glass plate

Publications (1)

Publication Number Publication Date
CN105579407A true CN105579407A (en) 2016-05-11

Family

ID=52743249

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201480053107.0A Pending CN105579407A (en) 2013-09-25 2014-09-22 Glass plate and chemically strengthened glass plate

Country Status (5)

Country Link
US (1) US20160200626A1 (en)
JP (1) JPWO2015046113A1 (en)
CN (1) CN105579407A (en)
TW (1) TW201518223A (en)
WO (1) WO2015046113A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102594924B1 (en) * 2015-10-29 2023-10-30 에이지씨 가부시키가이샤 Glass substrate for display, and method of manufacturing the glass substrate for display

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61205641A (en) * 1985-03-09 1986-09-11 Central Glass Co Ltd Chemical reinforcement of float glass
EP2371779A1 (en) * 2010-03-30 2011-10-05 Linde Aktiengesellschaft Method for producing flat glass and glass pane produced according to this method
WO2012141310A1 (en) * 2011-04-15 2012-10-18 旭硝子株式会社 Method for producing surface-treated glass substrate

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3981707A (en) * 1975-04-23 1976-09-21 Corning Glass Works Method of making fluorine out-diffused optical device
US4210386A (en) * 1975-04-23 1980-07-01 Corning Glass Works Fluorine out-diffused optical device and method
US6065309A (en) * 1997-09-20 2000-05-23 Wisconsin Alumni Research Foundation Float processing of high-temperature complex silicate glasses and float baths used for same
JP2006160546A (en) * 2004-12-06 2006-06-22 Hitachi Ltd Flat surface-type display device
US8778820B2 (en) * 2010-05-27 2014-07-15 Corning Incorporated Glasses having low softening temperatures and high toughness
WO2013082488A2 (en) * 2011-11-30 2013-06-06 Corning Incorporated Optical coating method, apparatus and product
US20160046519A1 (en) * 2013-04-08 2016-02-18 Nippon Sheet Glass Company Glass plate and process for manufacturing glass plate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61205641A (en) * 1985-03-09 1986-09-11 Central Glass Co Ltd Chemical reinforcement of float glass
EP2371779A1 (en) * 2010-03-30 2011-10-05 Linde Aktiengesellschaft Method for producing flat glass and glass pane produced according to this method
WO2012141310A1 (en) * 2011-04-15 2012-10-18 旭硝子株式会社 Method for producing surface-treated glass substrate

Also Published As

Publication number Publication date
US20160200626A1 (en) 2016-07-14
TW201518223A (en) 2015-05-16
JPWO2015046113A1 (en) 2017-03-09
WO2015046113A1 (en) 2015-04-02

Similar Documents

Publication Publication Date Title
CN104203858B (en) The glass plate of warpage when can reduce chemical enhanced
CN104203860B (en) The glass plate of warpage when can reduce chemical enhanced
CN105593177A (en) Glass plate production method
CN104884399A (en) Method for manufacturing glass plate with which warping during chemical strengthening is reduced and glass plate
CN105579408B (en) The manufacturing method of glass plate
US20180009707A1 (en) Glass sheet
US20160200623A1 (en) Glass sheet
JP6428630B2 (en) Glass plate
CN105612133A (en) Glass plate
CN105579407A (en) Glass plate and chemically strengthened glass plate
CN105579406A (en) Glass plate
WO2015046109A1 (en) Glass plate
WO2015046111A1 (en) Glass plate
WO2015046112A1 (en) Glass plate

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20160511